Method of manufacturing semiconductor device

Abstract

To provide a semiconductor device having improved performance while improving the throughput in the manufacturing steps of the semiconductor device. An insulating film portion comprised of first, second, third, fourth, and fifth insulating films is formed on a semiconductor substrate. The second insulating film is a first charge storage film and the fourth insulating film is a second charge storage film. The first charge storage film contains silicon and nitrogen; the third insulating film contains silicon and oxygen; and the second charge storage film contains silicon and nitrogen. The thickness of the third insulating film is smaller than that of the first charge storage film and the thickness of the second charge storage film is greater than that of the first charge storage film. The third insulating film is formed by treating the upper surface of the first charge storage film with a water-containing treatment liquid.

What is claimed is: 
     
       1. A method of manufacturing a semiconductor device, comprising the steps of:
 (a) providing a semiconductor substrate; 
 (b) forming an insulating film portion over the main surface of the semiconductor substrate; 
 (c) forming a conductive film over the insulating film portion; and 
 (d) patterning the conductive film and the insulating film portion, thereby forming a gate electrode, and a gate insulating film between the gate electrode and the semiconductor substrate, 
 wherein the step (b) comprises the steps of: 
 (b1) forming a first insulating film containing silicon and oxygen over the main surface of the semiconductor substrate; 
 (b2) forming a second insulating film containing silicon and nitrogen over the first insulating film; 
 (b3) forming a third insulating film containing silicon and oxygen over the second insulating film; 
 (b4) forming a fourth insulating film containing silicon and nitrogen over the third insulating film; 
 (b5) forming a fifth insulating film containing silicon and oxygen over the fourth insulating film, and thereby forming the insulating film portion comprised of the first insulating film, the second insulating film, the third insulating film, the fourth insulting film, and the fifth insulating film, 
 wherein a thickness of the third insulating film is smaller than a thickness of the second insulating film and a thickness of the fourth insulating film is greater than a thickness of the second insulating film, 
 wherein in the step (b2) the second insulating film is a silicon nitride film; 
 wherein in the step (b3), an upper surface of the second insulating film is directly treated with a first treatment liquid to form the third insulating film, and 
 wherein the first treatment liquid consists of pure water having a specific resistance at room temperature of at least 10 MΩcm. 
 
     
     
       2. The method of manufacturing a semiconductor device according to  claim 1 ,
 wherein in the step (b2), the second insulating film is formed by atomic layer deposition. 
 
     
     
       3. The method of manufacturing a semiconductor device according to  claim 1 ,
 wherein the gate electrode and the gate insulating film are parts of a nonvolatile memory configured such that 
 data are written in the nonvolatile memory by injecting electrons from the semiconductor substrate to the gate insulating film, and 
 data are erased from the nonvolatile memory by injecting holes from the semiconductor substrate to the gate insulating film. 
 
     
     
       4. The method of manufacturing a semiconductor device according to  claim 1 ,
 wherein the step (b3) comprises the steps of: 
 (b6) treating an upper surface of the second insulating film with the first treatment liquid; and 
 (b7) treating the upper surface of the second insulating film with a second treatment liquid containing hydrofluoric acid, 
 wherein in the step (b3), the step (b6) and the step (b7) are repeated alternately to form the third insulating film. 
 
     
     
       5. The method of manufacturing a semiconductor device according to  claim 1 ,
 wherein the first insulating film comprises silicon oxide, the third insulating film comprises silicon oxide, the fourth insulating film comprises silicon nitride, and the fifth insulating film comprises silicon oxide. 
 
     
     
       6. The method of manufacturing a semiconductor device according to  claim 1 ,
 wherein the second insulating film is a first charge storage film, and 
 wherein the fourth insulating film is a second charge storage film. 
 
     
     
       7. The method of manufacturing a semiconductor integrated circuit device according to  claim 2 ,
 wherein in the step (b2), the atomic layer deposition is conducted at a temperature less than 600° C. 
 
     
     
       8. The method of  claim 1 , wherein the pure water has a specific resistance of at least 18 MΩcm.